CN114618470A - Composite catalyst and preparation method and application thereof - Google Patents
Composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114618470A CN114618470A CN202011454008.7A CN202011454008A CN114618470A CN 114618470 A CN114618470 A CN 114618470A CN 202011454008 A CN202011454008 A CN 202011454008A CN 114618470 A CN114618470 A CN 114618470A
- Authority
- CN
- China
- Prior art keywords
- source
- gallium
- zinc
- aluminum
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001294 propane Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 22
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 20
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 150000001261 hydroxy acids Chemical class 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 11
- 229940044658 gallium nitrate Drugs 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CBIIVSNVIRRJAS-UHFFFAOYSA-N [C].CCC Chemical compound [C].CCC CBIIVSNVIRRJAS-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical group [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The application discloses a composite catalyst and a preparation method and application thereof. The application provides a low-cost and environment-friendly catalyst for preparing propylene by propane dehydrogenation; the catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.
Description
Technical Field
The application relates to a composite catalyst, a preparation method and application thereof, and belongs to the technical field of catalysts.
Background
Propylene is a basic chemical raw material and mainly comes from naphtha catalytic cracking, methanol-to-olefin, propane dehydrogenation and the like. Wherein propane dehydrogenation is developed more rapidly due to increased propane production and reduced costs.
At present, propane dehydrogenation catalysts are mainly Pt catalysts and Cr catalysts. The propane dehydrogenation process is limited by thermodynamics, and the reaction temperature has a serious influence on the conversion rate. In order to ensure the conversion rate of propane, the temperature of the propane dehydrogenation reaction is between 580 and 630 ℃. At this temperature, the carbon deposit inactivation of the catalyst is difficult to avoid, and the carbon burning regeneration of the catalyst is the main means for restoring the activity. However, the noble metal Pt is expensive, the chromium oxide has great toxicity to the environment and is difficult to bear the problems of catalyst breakage and loss, so that the circulating fluidized bed process cannot be adopted. The Pt catalyst mainly adopts a moving bed process, while the chromium oxide catalyst adopts a multi-reactor fixed bed reactor connected in parallel, and the operation process is complex and tedious. Therefore, the development of new catalysts with low cost and environmental friendliness is the main development direction of propane dehydrogenation catalysts.
Disclosure of Invention
Aiming at the problems, the invention provides a low-cost and environment-friendly composite catalyst for preparing propylene by propane dehydrogenation, and a preparation method and application thereof.
According to the first aspect of the application, a composite catalyst is provided, and is prepared by sequentially carrying out reaction I, drying and roasting on a mixture consisting of a zinc source, a gallium source, an aluminum source and hydroxy acid.
Optionally, the composite catalyst consists of four elements of zinc, gallium, aluminum and oxygen; the mass ratio of the zinc element to the gallium element to the aluminum element is 13.6-62.0: 0.6-7.8: 30.2 to 85.8.
Optionally, the hydroxy acid is selected from at least one of citric acid, tartaric acid, lactic acid and malic acid;
the zinc source is at least one selected from zinc nitrate, zinc chloride and zinc sulfate;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is selected from at least one of aluminum nitrate, aluminum chloride and aluminum sulfate.
According to a second aspect of the present application, there is provided a method for producing the above-mentioned composite catalyst, the method comprising:
(1) reacting a mixture consisting of a zinc source, a gallium source, an aluminum source and hydroxy acid I to obtain sol;
(2) and drying and roasting the material containing the sol to obtain the composite catalyst.
Optionally, in the step (1), the molar ratio of the zinc source to the gallium source to the aluminum source is 13.6 to 62.0: 0.6-7.8: 30.2-85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the moles of the aluminum source are based on the moles of the metallic aluminum; the moles of the zinc source are based on the moles of metallic zinc;
the molar ratio of the metal source to the hydroxy acid is 100: 10 to 100 parts;
the mole number of the metal source is the sum of the mole numbers of the zinc source, the gallium source and the aluminum source; the number of moles of the hydroxy acid is based on the number of moles of the hydroxy acid itself.
Optionally, the composite catalyst in the present application is prepared by a sol method.
Optionally, in the step (1), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
Specifically, the composite catalyst of the present application is not simply and physically mixed with zinc oxide, aluminum oxide and gallium oxide, but has a specific morphology and structure.
According to a final aspect of the present application, there is provided a process for producing propylene, the process comprising: reacting raw material gas containing propane in the presence of a catalyst to obtain propylene;
the catalyst is selected from at least one of the composite catalyst and the composite catalyst prepared by the method;
alternatively, the conditions of reaction II are: the reaction temperature is 530 ℃ and 630 ℃; the reaction space velocity is 200-600L Kg- 1h-1。
Alternatively, the pressure of reaction II is atmospheric pressure.
Optionally, the upper limit of the reaction temperature is independently selected from 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃ or 630 ℃; the lower limit is selected from 530 deg.C, 540 deg.C, 550 deg.C, 560 deg.C, 570 deg.C, 580 deg.C, 590 deg.C, 600 deg.C, 610 deg.C, 620 deg.C, or 625 deg.C.
Alternatively, the upper limit of the propane mass space velocity is selected from 220L Kg-1h-1、240L Kg-1h-1、260L Kg-1h-1、280L Kg-1h-1、300L Kg-1h-1、350L Kg-1h-1、400L Kg-1h-1、450L Kg-1h-1、500L Kg-1h-1、550L Kg-1h-1Or 600L Kg-1h-1(ii) a The lower limit is selected from 200L Kg-1h-1、220L Kg-1h-1、240L Kg-1h-1、260L Kg-1h-1、280L Kg- 1h-1、300L Kg-1h-1、350L Kg-1h-1、400L Kg-1h-1、450L Kg-1h-1、500L Kg-1h-1、550L Kg-1h-1Or 580L Kg-1h-1。
The beneficial effects that this application can produce include:
(1) the catalyst for preparing propylene by propane dehydrogenation is low in cost and environment-friendly;
(2) the catalyst can be applied to the development of a circulating fluidized bed process, and the development of a new propane dehydrogenation technology is promoted.
Drawings
FIG. 1 is an XRD pattern of catalyst 1;
fig. 2 is an XRD pattern of the mixed catalyst 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the raw materials and the products were detected by Agilent 7890B gas chromatography from Agilent, Inc., using PLOT-Q capillary column from Agilent, Inc.
In the examples of the present application, both propane conversion and propylene selectivity were calculated on a carbon mole basis.
The conversion, selectivity, in the examples of the present application were calculated as follows:
propane conversion ═ [ (moles of propane carbon in feed) - (moles of propane carbon in discharge) ]/(moles of propane carbon in feed) × (100%)
Propylene selectivity ═ propylene carbon moles on draw ]/[ (propane carbon moles on feed) - (propane carbon moles on draw) ] × (100%).
Example 1
2.01g of zinc nitrate, 0.191g of gallium nitrate, 1.5876g of aluminum nitrate and 0.5389g of lactic acid are weighed and added into 10ml of water, stirred at 20 ℃ until the zinc nitrate, the gallium nitrate, the 1.5876g of aluminum nitrate and the lactic acid are completely dissolved, and the stirring is continued for 300 minutes to obtain sol. Drying the sol at 80 ℃ for 18h, and roasting at 500 ℃ for 12h to obtain the catalyst 1. The XRD pattern of catalyst 1 is shown in fig. 1.
Example 2
1.1152g of zinc chloride, 0.1879g of gallium chloride, 0.9945g of aluminum chloride and 0.1832g of malic acid are weighed and added into 10ml of water, stirred at 50 ℃ until the materials are completely dissolved, and stirred for 60 minutes to obtain sol. Drying the sol at 50 ℃ for 20h, and roasting at 300 ℃ for 20h to obtain the catalyst 2.
Example 3
1.6445g of zinc nitrate, 0.2729g of gallium nitrate, 2.0889g of aluminum nitrate and 1.6673g of citric acid are weighed and added into 10ml of water, stirred at 30 ℃ until the materials are completely dissolved, and stirred for 240 minutes to obtain sol. Drying the sol at 150 ℃ for 10h, and roasting at 650 ℃ for 5h to obtain the catalyst 3.
Example 4
0.7064g of zinc sulfate, 0.0238g of gallium sulfate, 5.1635g of aluminum sulfate and 2.7106g of tartaric acid are weighed and added into 10ml of water, stirred at 80 ℃ until the materials are completely dissolved, and stirred for 30 minutes to obtain sol. Drying the sol at 200 ℃ for 4h, and roasting at 700 ℃ for 4h to obtain the catalyst 4.
Example 5
1.2791g of zinc nitrate, 0.0819g of gallium nitrate, 2.5067g of aluminum nitrate and 1.4759g of tartaric acid are weighed and added into 10ml of water, stirred at 50 ℃ until the materials are completely dissolved, and stirred for 60 minutes to obtain sol. Drying the sol at 110 ℃ for 12h, and roasting at 600 ℃ for 6h to obtain the catalyst 5.
Example 6
0.9136g of zinc nitrate, 0.0546g of gallium nitrate, 3.0498g of aluminum nitrate and 1.6523g of malic acid are weighed and added into 10ml of water, stirred at 60 ℃ until the materials are completely dissolved, and stirred for 40 minutes to obtain sol. Drying the sol at 100 ℃ for 12h, and roasting at 550 ℃ for 12h to obtain the catalyst 6.
Example 7
0.7309g of zinc nitrate, 0.0273g of gallium nitrate, 3.3005g of aluminum nitrate and 3.036g of citric acid are weighed into 10ml of water, stirred at 70 ℃ until the zinc nitrate, the gallium nitrate, the aluminum nitrate and the citric acid are completely dissolved, and stirring is continued for 30 minutes to obtain sol. Drying the sol at 200 ℃ for 4h, and roasting at 700 ℃ for 4h to obtain the catalyst 7.
Example 8
2.5216g of zinc nitrate, 0.2729g of gallium nitrate, 0.8774g of aluminum nitrate and 0.2461g of lactic acid are weighed and added into 10ml of water, stirred at 50 ℃ until the materials are completely dissolved, and stirred for 60 minutes to obtain sol. Drying the sol at 150 ℃ for 10h, and roasting at 600 ℃ for 6h to obtain the catalyst 8.
Comparative example 1
2.01g of zinc nitrate, 0.1804g of copper nitrate, 1.5876g of aluminum nitrate and 0.5389g of lactic acid are weighed and added into 10ml of water, stirred at 20 ℃ until the mixture is completely dissolved, and stirred for 300 minutes to obtain sol. The sol was dried at 80 ℃ for 18h and calcined at 500 ℃ for 12h to give comparative catalyst 1.
Comparative example 2
0.55g of zinc oxide powder, 0.07g of gallium oxide powder and 0.38g of aluminum oxide powder were weighed and physically mixed to obtain a mixed catalyst 1. Fig. 2 is an XRD pattern of the mixed catalyst 1. From the XRD results, it can be seen that catalyst 1 of example 1 and mixed catalyst 1 are completely different substances, i.e., catalyst 1 obtained in example 1 is not obtained by physical mixing of oxides.
Example 9
The catalysts of the foregoing examples and comparative examples were subjected to reaction evaluation: the catalyst is loaded into a fixed bed reactor, the reaction temperature is 530 ℃ and 630 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 200 ℃ to 630-600L Kg-1h-1. Samples were taken after 6min of reaction and the results are shown in Table 1.
TABLE 1 results of the catalytic reaction
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (8)
1. The composite catalyst is characterized in that a mixture consisting of a zinc source, a gallium source, an aluminum source and hydroxy acid is subjected to reaction I, drying and roasting in sequence to obtain the composite catalyst.
2. The hybrid catalyst according to claim 1, characterized in that the hybrid catalyst is composed of four elements of zinc, gallium, aluminum and oxygen; the molar ratio of the zinc element, the gallium element and the aluminum element is 13.6-62.0: 0.6-7.8: 30.2 to 85.8.
3. The composite catalyst according to claim 1, wherein the hydroxy acid is at least one selected from citric acid, tartaric acid, lactic acid, malic acid;
the zinc source is at least one selected from zinc nitrate, zinc chloride and zinc sulfate;
the gallium source is selected from at least one of gallium nitrate, gallium chloride and gallium sulfate;
the aluminum source is selected from at least one of aluminum nitrate, aluminum chloride and aluminum sulfate.
4. A method for producing a hybrid catalyst according to any one of claims 1 to 3, characterized by comprising:
(1) reacting a mixture consisting of a zinc source, a gallium source, an aluminum source and hydroxy acid I to obtain sol;
(2) and drying and roasting the material containing the sol to obtain the composite catalyst.
5. The method according to claim 4, wherein in the step (1), the molar ratio of the zinc source to the gallium source to the aluminum source is 13.6 to 62.0: 0.6-7.8: 30.2-85.8;
the mole number of the gallium source is calculated by the mole number of the metal gallium; the moles of the aluminum source are based on the moles of the metallic aluminum; the moles of the zinc source are based on the moles of metallic zinc;
the molar ratio of the metal source to the hydroxy acid is 100: 10 to 100 parts;
the mole number of the metal source is the sum of the mole numbers of the zinc source, the gallium source and the aluminum source; the number of moles of the hydroxy acid is based on the number of moles of the hydroxy acid itself.
6. The production method according to claim 4, wherein in the step (1), the conditions of the reaction I are: the temperature is 20-80 ℃; the time is 0.5-5 h;
in the step (2), the drying conditions are as follows: the temperature is 50-200 ℃; the time is 4-20 h;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 4-20 h.
7. A process for producing propylene, comprising: reacting raw material gas containing propane in the presence of a catalyst to obtain propylene;
the catalyst is selected from at least one of the composite catalyst according to any one of claims 1 to 3 and the composite catalyst prepared by the method according to any one of claims 4 to 6.
8. The method according to claim 7, wherein the conditions of the reaction II are as follows: the reaction temperature is 530 ℃ and 630 ℃; the reaction space velocity is 200-600L Kg-1h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011454008.7A CN114618470B (en) | 2020-12-10 | Composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011454008.7A CN114618470B (en) | 2020-12-10 | Composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114618470A true CN114618470A (en) | 2022-06-14 |
| CN114618470B CN114618470B (en) | 2023-11-17 |
Family
ID=
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618463A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473654A (en) * | 2002-08-06 | 2004-02-11 | 中国科学院大连化学物理研究所 | Composite oxide catalyst and its preparing method and use |
| CN101745405A (en) * | 2009-12-17 | 2010-06-23 | 汕头大学 | Perovskite type composite oxide catalyst for purifying tail gas of internal combustion engine |
| US20130006030A1 (en) * | 2011-06-28 | 2013-01-03 | King Fahd University Of Petroleum And Minerals | Oxidative dehydrogenation of propane |
| US20130165729A1 (en) * | 2011-12-22 | 2013-06-27 | Saudi Basic Industries Corporation | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
| CN111253204A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene by ethanol dehydration |
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473654A (en) * | 2002-08-06 | 2004-02-11 | 中国科学院大连化学物理研究所 | Composite oxide catalyst and its preparing method and use |
| CN101745405A (en) * | 2009-12-17 | 2010-06-23 | 汕头大学 | Perovskite type composite oxide catalyst for purifying tail gas of internal combustion engine |
| US20130006030A1 (en) * | 2011-06-28 | 2013-01-03 | King Fahd University Of Petroleum And Minerals | Oxidative dehydrogenation of propane |
| US20130165729A1 (en) * | 2011-12-22 | 2013-06-27 | Saudi Basic Industries Corporation | Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
| CN111253204A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing ethylene by ethanol dehydration |
Non-Patent Citations (2)
| Title |
|---|
| ENES KILINC ET.AL: "High temperature thermopower of sol–gel processed Zn1−x−yAlxMeyO (Me: Ga, In)", 《J MATER SCI: MATER ELECTRON》 * |
| 吴同旭等: "CrOx/Al2O3丙烷脱氢催化剂性能研究", 《天然气化工(C1化学与化工)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618463A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
| CN114618463B (en) * | 2020-12-10 | 2023-11-17 | 中国科学院大连化学物理研究所 | Composite catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101896267B (en) | Mixed manganese ferrite catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof | |
| AU2013203123B2 (en) | Treating of catalyst support | |
| CN105817222B (en) | A kind of preparation method and application of hydro carbons catalyst for fischer-tropsch synthesis composition | |
| CN105921147B (en) | A kind of hydro carbons catalyst for fischer-tropsch synthesis composition and its application | |
| CN110152650A (en) | A kind of preparing propylene by dehydrogenating propane supported catalyst and preparation method thereof | |
| CN101966460B (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| Saito et al. | Dehydrogenation of ethane via the Mars–van Krevelen mechanism over La0. 8Ba0. 2MnO3− δ perovskites under anaerobic conditions | |
| CN107073455B (en) | Improved selective ammonia oxidation catalyst | |
| CN109939693B (en) | CoMn2O4Bimetallic oxide catalyst, preparation method and application | |
| CN104549321B (en) | Catalyst for dehydrogenation of low-carbon paraffin and application thereof | |
| CN104549302B (en) | Ferrate catalyst as well as preparation method and application thereof | |
| CN114931968A (en) | Catalyst for preparing olefin by low-carbon alkane dehydrogenation and application thereof | |
| CN112705218B (en) | Catalyst for preparing low-carbon olefin from synthesis gas, preparation method and application thereof | |
| CN108246293A (en) | Dehydrating alkanes alkene catalyst, preparation method and application | |
| CN114618470A (en) | Composite catalyst and preparation method and application thereof | |
| CN114618470B (en) | Composite catalyst and preparation method and application thereof | |
| CN103274887B (en) | Method for synthesizing 1,3-butadiene by using Bi/Mo/Ce three-component composite oxide catalyst | |
| CN113398912B (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN107614106B (en) | Catalyst for oxidative dehydrogenation and preparation method thereof | |
| CN106000448B (en) | Vinyltoluene production catalyst and preparation method thereof | |
| CN114618463B (en) | Composite catalyst and preparation method and application thereof | |
| CN108101872A (en) | A kind of grading method of catalyst of n butane oxidation production cis-butenedioic anhydride | |
| CN112237918A (en) | Dual-function supported catalyst for oxidative dehydrogenation and dry reforming of low-carbon alkane and preparation method thereof | |
| CN109701632B (en) | Catalyst for preparing low-carbon hydrocarbon from synthetic gas and application thereof | |
| CN105916579A (en) | Butadiene production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |